JP3885100B2 - Multi-component composite film and method for producing the same - Google Patents

Multi-component composite film and method for producing the same Download PDF

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JP3885100B2
JP3885100B2 JP2002520328A JP2002520328A JP3885100B2 JP 3885100 B2 JP3885100 B2 JP 3885100B2 JP 2002520328 A JP2002520328 A JP 2002520328A JP 2002520328 A JP2002520328 A JP 2002520328A JP 3885100 B2 JP3885100 B2 JP 3885100B2
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film
support layer
separation membrane
polymer
producing
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JP2004506542A (en
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ソン−ジン・イ
ヒャン−モク・イ
スン−ホ・アン
ジン−ヨン・チョ
ヒュン−ハン・ヨン
ヒュン−コン・イ
サン−ヨン・イ
ホン−シク・ソン
スン−ヨン・パク
ユ−ジン・キュン
ビョン−イン・アン
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エルジー・ケミカル・カンパニー・リミテッド
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D67/0081—After-treatment of organic or inorganic membranes
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Description

【０００１】
【発明の属する技術分野】
本発明は多成分系複合フィルム及びその製造方法に関し、特に、電気化学素子用高分子電解質として利用できる多成分系複合フィルム及びその製造方法と、それを適用した高分子電解質システムに関する。
【０００２】
【従来の技術】
最近、エネルギー保存技術に対する関心が高まっている。例えば、携帯電話、カムコーダ、ノートブックコンピュータ、及び電気自動車等におけるエネルギー保存技術は重要であるので、エネルギー保存手段の一種である電池に対する研究、開発が活発に行われており、その中でも充放電が可能な二次電池は関心の焦点となっている。最近では、電池を開発するにあたってその性能を向上させ、電池製作工程の収率と経済性を高めるために新たな電極と高分子電解質を開発するための研究が絶えず進められている。特に、新たな高分子電解質に対する開発は安全性が向上した新たな高性能電池の創出という観点から大きな関心となっている。
【０００３】
電解質は大きく液体電解質と固体電解質の２種類に分類できる。液体電解質とは塩が有機溶媒に溶解、解離されて正極と負極との間でイオン伝導できるものであって、イオンの伝導度が高いという長所を持っている。しかし、液体電解質は、実際電池に高分子分離膜と共に用いられるが、例えば、ポリオレフィン類のような高分子フィルム内部に微細多孔構造を作ってその気孔内部に液体電解質を満たしてイオン伝導性を有するようにする。高分子分離膜が有する気孔率とその構造によって差異はあるが、この場合イオンの伝導度は約１ｍＳ／ｃｍ程度となる。しかし、気孔内部に存在する液体電解質の高い流動性によって非正常状態である時、高分子分離膜外に液体電解質が容易に滲みでたり洩れたりする問題を招くことがある。しかも、電極との界面形成においてそれらの間が接着されていないため常に単純接触で電池を構成しなければならない短所がある。長所は高分子分離膜自体が高い結晶化度を有しているので、優れた機械的強度を有していて、液体電解質による影響が殆どないために決して過度に膨潤されたり分解されたりしないということである。
【０００４】
その反面、固体電解質の場合、常温でのイオンの伝導度が電池の性能実現に十分でないという短所がある。これを解決するために、塩が有機溶媒に溶解された状態の液体電解質が固体高分子電解質に含浸された状態のゲル化性高分子電解質が利用されているが、その例としてベルコア（Bellcore）社で開発したハイブリッド型（米国特許第５，４１８，０９１号）がある。しかし、ゲル型高分子電解質の場合、機械的強度が低い短所があって電池組立上の問題点を有し、電極間の絶縁を維持し工程上要求される機械的強度のためにゲル型高分子電解質の厚さは一般に５０μｍを超えるものでなければならないが、このような高分子電解質の厚さはゲル型高分子の過度な膨潤による厚さ増加など非正常的な問題を誘発し、体積の増加によるエネルギー密度の減少などの問題を招く。以上に言及した問題点の他にまた、環境的に問題となる低分子量の可塑剤の使用と抽出工程の負担が量産における大きな障害となっている。
【０００５】
高分子電解質が備えなければならない条件としては、作動電圧範囲内で電気化学的安定性と熱的、化学的安定性がある。常温でのイオンの伝導度は電池作動上１ｍＳ/ｃｍを超えるものでなければならず、非水系電解液の場合より含浸性及び耐化学性が優れていなければならない。また、電池組立時に電極との界面抵抗を減少させるために接着性がなければならず、組立工程時に要求される充分な機械的強度も要求される。しかし、一般的な場合、イオンの伝導度を向上させると機械的物性が悪くなり、機械的物性を良くするとイオン電導度が減少する問題点がある。
【０００６】
上記のイオンの伝導度と機械的物性が相反する問題を解決するために多孔質高分子層とゲル化性高分子の多層構造フィルムを利用して電池の分離膜として使用することが提案されたことがある（米国特許第５，６３９，５７３号、第５，７１６，４２１号、第５，６３１，１０３号、第５，８４９，４３３号、ヨーロッパ公開特許公報第０９３３８２４Ａ２号）。ここで、多孔質高分子は液体電解液を気孔内部に限定的に吸収していて殆ど膨潤していない物質であって、たとえばポリエチレン（polyethylene）、ポリプロピレン（polypropylene）、ポリテトラフルオロエチレン（polytetrafluoroethylene）、ポリエチレンテレフタレート（polyethylene terephthalate）、ポリブチレンテレフタレート（polybutyleneterephthalate）、ポリエチレンナフタレート（polyethylenenaphthalate）などとそれらのフィルムの組み合わせによって製造される多層あるいはブレンドフィルムである。ゲル化性高分子は液体電解質と接触する場合、自らゲル化して膨潤する高分子を意味し、たとえば、ポリフッ化ビニリデン（polyvinylidenefluoride）、ポリウレタン（polyurethane）、ポリエチレンオキシド（polyethyleneoxide）、ポリアクリロニトリル（polyacrylonitrile）、ポリメチルメタクリレート（polymethylmethacrylate）、ポリアクリルアミド（polycrylamide）、ポリビニルアセテート（polyvinylacetate）、ポリビニルピロリジノン（polyvinylpyrrolidinone）、ポリテトラエチレングリコールジアクリレート（polytetracthylene glycol diacrylate）及びこのような高分子の共重合体などが使用できる。
【０００７】
【発明が解決しようとする課題】
このような構造は機械的物性を向上させることはできるが、ゲル化性高分子の抗イオン伝導性によって多孔質高分子層とこれに含浸された液体電解質だけのイオンの伝導度に比べて低いイオン伝導性を有することになる。従って、イオンの伝導度の向上のためにジブチルフタレート（dibutyl phthalate）のような低分子量の可塑剤の利用が要求される（米国特許第５，６３１，１０３号、米国特許第５，８４９，４３３号）。しかし、可塑剤の利用は上述したように多様な問題点を招く。また、このような方法によって製造された多層構造フィルムの場合、多孔質高分子層の外面に存在するゲル化高分子層が気孔のない緻密な構造になっていてイオン電導抵抗が大きく、二つの層間の界面接着力が弱くなる短所がある。
【０００８】
本発明は前記従来技術の問題点を考慮して、電気化学的安定性、電極との接着性、電解液含浸性及び安定性などが満足されながら可塑剤を抽出したり除去したりする工程なく製造され、イオンの伝導度と機械的物性を同時に満足させる多成分系複合フィルム、その製造方法、及びこの多成分系複合フィルムを利用する高分子電解質システムを提供することを目的とする。
【０００９】
【課題を解決するための手段】
本発明は前記目的を達成するために、多成分系複合フィルムにおいて、
ａ）高分子支持層（support layer）フィルム;及び
ｂ）前記フィルムの一面または両面に形成される多孔質ゲル化性高分子層（gellable polymer layer）
を含み、前記ａ）成分である支持層フィルムとｂ）成分である多孔質ゲル化性高分子層は界面なく一体化している多成分系複合フィルムを提供する。
【００１０】
また、本発明は前記多成分系複合フィルムの製造方法において、
ａ）高分子支持層フィルムを製造する段階;
ｂ）ゲル化性高分子を溶媒に溶解してゲル化性高分子溶液を製造する段階;
ｃ）前記ｂ）段階のゲル化性高分子溶液を前記ａ）段階の支持層フィルムの一面または両面に塗布してゲル化性高分子層を形成し多層フィルムを製造する段階;及び
ｄ）前記ｃ）段階の多層フィルムを延伸した後、熱固定する段階
を含む支持層フィルムとゲル化性高分子層が界面なく一体化している多成分系複合フィルムの製造方法を提供する。
【００１１】
また、本発明は前記多成分系複合フィルムを分離膜として利用する高分子電解質システム、及びこれを含む電気化学素子を提供する。
【００１２】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００１３】
本発明は従来の一定の大きさの気孔を有する微細気孔膜上にゲル化性高分子液を塗布して製造する気孔膜とゲル化性高分子物質が界面を有する高分子電解質用多層フィルムとは異なって、気孔を全く有しない一般的な高分子フィルム上にゲル化性高分子物質を塗布して高分子フィルム上にゲル化性高分子層を形成した後、高温延伸して気孔を形成させることによって高分子フィルムとゲル化性高分子層の間に界面が形成されずに一体化した多成分系複合フィルムを製造する。
【００１４】
このように高分子フィルム（高分子支持層）とゲル化性高分子物質（多孔質ゲル化性高分子層）の間に界面が形成されずに一体化することは延伸工程の高温で相互拡散（inter-diffusion）によるものであり、支持層とゲル化性高分子層の高分子間に相互結合が増大して各々を離しがたい程度に一体化する。具体的には、本発明の多成分系複合フィルムをＪＩＳ Ｚ ０２３７の方法で界面接着力を測定すれば、少なくとも１００ｇｆ以上の界面接着力を有し、好ましくは少なくとも１５０ｇｆ以上を有する。
【００１５】
また、前記多成分系複合フィルムを適用した電気化学素子用高分子電解質システムはこのような多成分系複合フィルムに塩、及び有機溶媒を含有する液体電解質を含浸することで実現される。特に、このような高分子電解質システムは電池のような電気化学素子において支持層一面または両面に塗布されるゲル化性高分子物質単独、またはゲル化性高分子と塩とが配位結合して形成される高分子−塩の錯体を電解質として利用できるようになる。
【００１６】
以下、前記多成分系複合フィルムの構成について説明する。
【００１７】
前記ａ）の支持層フィルムは高密度ポリエチレン（high density polyethylene）、低密度ポリエチレン（low density polyethylene）、線状低密度ポリエチレン（linear low density polyethylene）、ポリプロピレン（polypropylene）、高結晶性ポリプロピレン（high crystalline polypropylene）、ポリエチレン−プロピレン共重合体（polyethylene-propylene copolymer）、ポリエチレン−ブチレン共重合体（polyethylene-butylene copolymer）、ポリエチレン−ヘキセン共重合体（polyethylene-hexene copolymer）、ポリエチレン−オクテン共重合体（polyethylene-octene copolymer）、ポリスチレン−ブチレン−スチレン共重合体（polystyrene-butylene-styrene copolymer）、ポリスチレン−エチレン−ブチレン−スチレン共重合体（polystyrene-ethylene-butylene-styrene copolymer）、ポリスチレン（polystyrene）、ポリフェニレンオキシド（polyphenylene oxide）、ポリスルホン（polysulfone）、ポリカーボネート（polycarbonate）、ポリエステル（polyester）、ポリアミド（polyamide）、ポリウレタン（polyurethane）、ポリアクリレート（polyacrylate）、ポリ塩化ビニリデン（polyvinylidene chloride）、ポリフッ化ビニリデン（polyvinylidene fluoride）、ポリシロキサン（polysiloxane）、ポリオレフィンアイオノマー（polyolefin ionomer）、ポリメチルペンテン（polymethyl pentene）、水素添加オリゴシクロペンタジエン（hydrogenated oligocyclopentadiene, HOCP）、及びこれらの共重合体または誘導体からなる群より１種以上選択される高分子がブレンド、または積層（lamination）形態で製造されるのが好ましい。
【００１８】
特に、前記高結晶性ポリプロピレンは密度０．９０５ｇ/ｃｃ以上、溶融温度１６４℃以上、結晶化温度１２５℃以上、結晶化度５０％以上、アイソタクチシティ（またはペンタド比率）９６％以上、及びアタクチック比率５％未満の条件の中で１種以上の条件を満足するのが好ましい。
【００１９】
前記ｂ）のゲル化性高分子層はその材質が多成分系複合フィルムの用途によって選択されるが、一般的にポリフッ化ビニリデン、ポリフッ化ビニリデン−三フッ化塩化エチレン共重合体（polyvinylidene fluoride-chlorotrifluoroethylene copolymer）、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体（polyvinyliden fluoride-hexafluoropropylene copolymer）、ポリエチレンオキシド（polyethylene oxide）、ポリプロピレンオキシド（polypropylene oxide）、ポリブチレンオキシド（polybutylene oxide）、ポリウレタン（polyurethane）、ポリアクリロニトリル（polyacrylonitrile）、ポリアクリレート（polyacrylate）、ポリメチルメタクリレート（polymethyl methacrylate）、ポリアクリル酸（polyacrylic acid）、ポリアミド（polyamide）、ポリアクリルアミド（polyacrylamide）、ポリビニルアセテート（polyvinyl acetate）、ポリビニルピロリドン（polyvinylpyrrolidone）、ポリテトラエチレングリコールジアクリレート（polytetraethylene glycol diacrylate）、ポリスルホン（polysulfone）、ポリフェニレンオキシド（polyphenylene oxide）、ポリカーボネート（polycarbonate）、ポリエステル（polyester）、ポリ塩化ビニリデン（polyvinylidene chloride）、ポリシロキサン（polysiloxane）、ポリオレフィンアイオノマー（polyolefin ionomer）、及びこれらの共重合体または誘導体からなる群より１種以上選択される。
【００２０】
前記ゲル化性高分子層は陰イオンの固定によるイオン転移数（ion transference number）を向上させるために高分子−リチウム塩の錯体を含有するのが好ましい。従って、電子を与えることができる元素とリチウムイオンの配位結合を形成するのに関与する溶解エネルギーがリチウムの格子（lattice）エネルギーより大きい物質としてＬｉＳＣＮ、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＡｓＦ6、ＬｉＮ（ＣＦ3ＳＯ2）2、及びＬｉＢＦ4からなる群より１種以上選択されるリチウム塩をさらに含むことができる。
【００２１】
また、前記ゲル化性高分子層はイオン転移数をさらに向上させるためにシリカ（SiO2）、酸化チタン（TiO2）、アルミナ（Al2O3）、酸化マグネシウム（MgO）、及び酸化バリウム（B2O3）からなる群より１種以上選択される多孔質無機粒子をさらに含むことができる。
【００２２】
以下、前記多成分系複合フィルムの製造方法について説明する。
【００２３】
本発明の多成分系複合フィルムは上述した様々な材質の支持層フィルムの一面または両面に前記で説明したゲル化性高分子を溶媒に溶解した溶液でゲル化性高分子層を形成させ、これを延伸してフィルムに気孔を形成させることによって高分子フィルムとゲル化性高分子物質の間に界面が形成されず一体化して製造する。この時、支持層フィルムの他にゲル化性高分子層にも気孔が形成される。
【００２４】
前記ａ）段階の支持層フィルムは上述した高分子をＴ−ダイ（T-die）または管状ダイ（tubular die）が設けられた押出機（extruder）で押出した後、結晶化度及び弾性復元率を高めるために乾燥オーブンで常温乃至最大高分子の最高融点の温度下でアニーリング（annealing）して製造することが好ましい。
【００２５】
また、このような支持層フィルムは、ゲル化性高分子層との界面接着力をさらに向上させるために反応性ガス導入下でイオンビームを照射することも可能である。このようなイオンビーム照射は一種の表面改質方法であって、フィルムのアニーリング前あるいは後の全てに適用でき、最終多成分系複合フィルムの物性によってその実施の可否を判断する。
【００２６】
前記反応性ガス導入下のイオンビーム照射工程を具体的に説明すると、１０-1乃至１０-6ｔｏｒｒ程度の高真空に維持された真空槽内に支持層フィルム１１を投入した後、イオン銃に電子、水素、ヘリウム、酸素、窒素、二酸化炭素、空気、フッ化物、ネオン、アルゴン、クリプトン、及びＮ2Ｏからなる群より１種以上選択されるイオン生成ガスを注入して０．０１乃至１０6ｋｅＶ程度のエネルギーを有する粒子を生成させた後、イオンビーム電流を変化させながらエネルギーを有する粒子を支持層フィルムの一側面または両側面に照射する。このようなイオンビームを照射する時、イオン粒子の照射量は１０5乃至１０20ｉｏｎｓ/ｃｍ2が好ましい。また、イオンビーム照射と同時にフィルム周囲にヘリウム、水素、酸素、窒素、アンモニア、一酸化炭素、二酸化炭素、クロロフルオロ、メタン、及びＮ2Ｏからなる群より１種以上選択される反応性ガスを反応性ガス注入器によって０．５乃至２０ｍｌ/分の注入量で注入して表面を改質する。
【００２７】
本発明の多成分系複合フィルムは前記支持層フィルムの一面または両面にゲル化性高分子の溶液を使ってゲル化性高分子層を形成させる。このゲル化性高分子溶液は上述したゲル化性高分子を溶媒に溶解することによって製造される。
【００２８】
前記溶媒は１−メチル−２−ピロリドン（NMP）、アセトン、エタノール、ｎ−プロパノール、ｎ−ブタノール、ｎ−ヘキサン、シクロヘキサノール、酢酸、酢酸エチル、ジエチルエーテル、ジメチルホルムアミド（DMF）、ジメチルアセトアミド（DMAc）、ジオキサン、テトラヒドロフラン（THF）、ジメチルスルホキシド（DMSO）、シクロヘキサン、ベンゼン、トルエン、キシレン、及び水からなる群より１種以上選択される単独溶媒または混合溶媒である。このようなゲル化性高分子溶液の濃度及び塗布条件は使用物質によって多様に変化できるが、特に濃度は０．０１乃至９０重量％が好ましい。また、このようなゲル化性高分子溶液は製造する時に上述したリチウム塩、無機多孔質粒子、またはこれらの混合物をゲル化性高分子と共に投入してもよい。
【００２９】
ゲル化性高分子層の形成は二つの方法で実施できる。一つの方法は、前記ゲル化性高分子溶液を支持層フィルムに塗布した後、適切な条件で乾燥して層状に作る方法である。また、他の一つの方法はゲル化性高分子溶液を離型紙または離型フィルム上に塗布した後、第１の方法と類似した条件で乾燥してフィルム形態に製造しこれを離型フィルムから剥離して支持層フィルム上に位置させた後、ラミネータ等で熱接着する方法である。この時の熱接着は支持層フィルム材質とゲル化性高分子の熱融着温度を考慮して選択すれば容易に接着できる。つまり、常温乃至支持層またはゲル化性高分子層の高分子融点の温度で行う。
【００３０】
前記工程の具体的な製造過程は下記の通りである。
【００３１】
前記ゲル化性高分子溶液を支持層フィルムに塗布した後、適切な条件で乾燥して薄膜形態に作った後、延伸する第１の方法は、
ａ）支持層として用いられる高分子を押出機に投入してフィルム前駆体を製造する段階;
ｂ）前記製造されたフィルム前駆体を高分子の融点以下の温度でアニーリングする段階;
ｃ）必要な時、前記アニーリングしたフィルム前駆体の一面または両面に反応性ガスの助けによるイオンビームを照射する段階;
ｄ）前記イオンビームを照射されたフィルム前駆体の一面または両面にゲル化性高分子溶液を塗布する段階;
ｅ）前記フィルム前駆体の一面または両面に塗布された高分子溶液を乾燥する段階;
ｆ）前記高分子溶液が乾燥されたフィルム前駆体を常温以下の温度で低温延伸する段階;
ｇ）前記低温延伸されたフィルム前駆体を高分子の融点以下の温度で高温延伸する段階;及び
ｈ）前記高温延伸されたフィルム前駆体を高分子の融点以下の温度で張力が与えられた状態で熱固定する段階
を含む。
【００３２】
ゲル化性高分子溶液を離型紙または離型フィルム上に塗布してこれを支持層フィルムに熱接着した後、延伸する他の方法は
ａ）支持層として用いられる高分子を押出機に投入してフィルム前駆体を製造する段階;
ｂ）前記製造されたフィルム前駆体を高分子の融点以下の温度でアニーリングする段階;ｃ）必要な時、前記アニーリングしたフィルム前駆体の一面または両面に反応性ガスの助けによるイオンビームを照射する段階;
ｄ）ゲル化性高分子溶液を離型紙又は離型フィルム上に塗布する段階;
ｅ）前記離型フィルム上に塗布された高分子溶液を乾燥する段階;
ｆ）前記乾燥されたゲル化性高分子層フィルムを離型フィルムから剥離した後、前記フィルム前駆体の一面または両面に熱接着する段階;
ｇ）前記ゲル化性高分子フィルムが熱接着されたフィルム前駆体を常温以下の温度で低温延伸する段階;
ｈ）前記低温延伸されたフィルム前駆体を高分子の融点以下の温度で高温延伸する段階;及び
ｉ）前記高温延伸されたフィルム前駆体を高分子の融点以下の温度で張力が与えられた状態で熱固定する段階
を含む。
【００３３】
前記ゲル化性高分子溶液を支持層フィルムに直接塗布したり離型紙または離型フィルムに塗布する方法はディップコーティング（Dip coating）、噴射コーティング（Spray coating）、スピンコーティング（Spin coating）、ダイコーティング（Die coating）、ロールコーティング（Roll coating）などの方式で実施することができ、特にいずれかに制限されるものではない。塗布の厚さは最終多成分系複合フィルムの用途によって異なるが、支持層フィルムの厚さが１乃至５０μｍであれば、乾燥後、ゲル化性高分子層の厚さが０．０１乃至２５μｍになるようにするのが好ましい。
【００３４】
このような塗布はフィルムのアニーリング前もしくは後、または前及び後で実施でき、多成分系複合フィルムの物性によって塗布過程の前に反応性ガスの助けによるイオンビーム照射過程を行うことができる。
【００３５】
塗布されたゲル化性高分子溶液の乾燥は、ゲル化性高分子溶液の溶媒飽和蒸気圧以下で窒素、酸素、二酸化炭素、及び空気からなる群より１種以上選択されるガスで囲まれた雰囲気下で実施するのが好ましく、湿度は相対湿度で１乃至１００％の条件下で実施されることが好ましい。
【００３６】
本発明の多成分系複合フィルムは支持層フィルムの一面または両面にゲル化性高分子層が形成された後、支持層フィルムと支持層フィルムの一面または両面に塗布されたゲル化性高分子層に気孔が形成される。
【００３７】
一般的に、高分子フィルムに気孔を形成させる方法は相転移法と乾式法がある。相転移法は高分子溶液を作った後、温度または非溶媒などを適切に使用して高分子と溶媒との相転移を起こして気孔を形成する方法で、相転移条件によって製造されたフィルムの特性が決められる。また、乾式法は高分子結晶部分を一定の方向に配向させた後、冷延伸によって相対的に弱い無定形部分を破裂させ気孔を形成する方法であって、結晶部分の均一な配向及び程度によって製造されたフィルムの特性が決められる。
【００３８】
本発明では適切な気孔形成のために支持層フィルムの一面または両面にゲル化性高分子層が形成された後に延伸する。この時、支持層及びゲル化性高分子層各々の気孔の大きさ及び分布は互いに異なる。これを説明すると、支持層は、フィルム前駆体はその製造工程で結晶構造が一定の方向に配向された後、前記延伸によって気孔が形成されるのである。一方、ゲル化性高分子層には相転移法および乾式法によって気孔が形成されるのであるが、その際は、ゲル化性高分子層にはゲル化性高分子と溶媒間での相転移により微細気孔ないし微細亀裂が生じるのであって、その気孔の径ないし亀裂の大きさは延伸処理によって大きくなるのである。特に、ゲル化性高分子層は相転移条件によって緻密な構造、微細亀裂または微細気孔などの多様な形態を延伸前に形成することができ、また、その形成程度が調節できる。
【００３９】
従って、支持層の気孔とゲル化性高分子層の気孔は、製造工程上の差異によって気孔の大きさ及び分布が異なるものとなる。
【００４０】
前記延伸は低温延伸工程と高温延伸工程を含む。
【００４１】
前記低温延伸は、支持層フィルムの一面または両面にゲル化性高分子層が形成された多層フィルムをロールまたはその他の延伸機を利用して０乃至５０℃の温度条件下で１軸延伸して支持層に微細亀裂を生成させてゲル化性高分子層１２に既に形成された気孔の大きさを拡大する。
【００４２】
前記高温延伸は、前記低温延伸によって形成された微細亀裂をロールまたはその他の延伸機を利用して５０℃乃至最大支持層またはゲル化性高分子層の高分子の融点の温度条件下で１軸または２軸延伸し、所望の大きさを有する微細気孔を形成し、また、このような高温延伸を通じて膜に機械的物性を付与する。
【００４３】
前記のように低温及び高温延伸された多層フィルムは延伸後、熱固定を行う。このような熱固定は５０℃乃至最大支持層またはゲル化性高分子層の高分子の融点の温度条件下で張力を受けた状態そのまま１０秒乃至１時間の一定の時間実施されるが、この過程を通じて最終的に支持層フィルムとゲル化性高分子層を含む多成分系複合フィルムが製造される。
【００４４】
本発明の多成分系複合フィルムは、前記高温延伸及び熱固定段階を通じて、支持層フィルムとゲル化性高分子層の間の高分子鎖の相互拡散（inter-diffusion）が増大して支持層フィルムとゲル化性高分子層の間の界面接着力が増加し、これによって支持層とゲル化性高分子層の界面が不明確になって一体化する。特に、既述したが、支持層フィルムを反応性ガス導入下でイオンビーム照射をすると、このような界面の接着力はさらに増加する。
【００４５】
前記高温延伸と熱固定段階を経た後の多成分系複合フィルムは、支持層フィルムにおいて気孔の大きさが０．００１乃至１０μｍで、厚さが１乃至５０μｍであり、支持層フィルムの一面または両面に位置する多孔質ゲル化性高分子層は、気孔の大きさが最大１０μｍ、厚さが０．０１乃至２５μｍであり、これを高分子電解質システム、または電気化学素子などに使用することが好適である。
【００４６】
図１は、このような本発明の多成分系複合フィルムの構造の一例であって、支持層フィルム１１の両面にゲル化性高分子層１２が位置した図面である。この時、上記の多成分系複合フィルム製造工程のうち支持層フィルム１１表面にゲル化性高分子層１２を塗布した後に実施される延伸及び熱固定過程によって支持層フィルム１１とゲル化性高分子層１２間の界面１３が不明確となったことを示す。また、このような界面なく一体化した多成分系複合フィルムは優れたイオン伝導性、及び電気化学的安定性を有する。
【００４７】
本発明の多成分系複合フィルムの製造方法は、各々の段階が所望の最終用途によって一部段階を省略したり追加工程を付加したりすることができ、各段階のうち一部はその順序も変更できる。
【００４８】
本発明の多成分系複合フィルムは、様々な分離膜たとえば、微細ろ過膜（microfiltration membrane）、限外ろ過膜（ultrafiltration membrane）、気体分離膜（gas separation）、透過蒸発膜（pervaporation membrane）、逆浸透膜（reverse osmosis membrane）、電気化学素子用分離膜に用いることができる。特に、高分子電解質システムでは電気化学的安定性、電極との接着性、電解液含浸性及び安定性を付与することができる。
【００４９】
本発明は
ａ）ｉ）多孔質支持層フィルム;及び
ｉｉ）前記ｉ）支持層フィルムの一面または両面に形成される多孔質ゲル化性高分子層を含み、前記ｉ）の支持層フィルムとｉｉ）の多孔質ゲル化性高分子層は界面なく一体化している多成分系複合フィルムの分離膜;及び
ｂ）ｉ）下記の化学式２で示される塩;及び
ｉｉ）有機溶媒
を含む液体電解質
を含む高分子電解質システムを提供する。
【００５０】
[化学式２]
Ａ+Ｂ-
前記式において、
Ａ+はＬｉ+、Ｎａ+、及びＫ+からなるアルカリ金属陽イオン群、及びこれらの誘導体から１種以上選択され、
Ｂ-はＰＦ6 -、ＢＦ4 -、Ｃｌ-、Ｂｒ-、Ｉ-、ＡｓＦ6 -、ＣＨ3ＣＯ2 -、ＣＦ3ＳＯ3 -、Ｎ（ＣＨ3ＳＯ2）2 -、及びＣ（ＣＨ3ＳＯ2）3 -からなる群より１種以上選択される。
【００５１】
前記ａ）の多成分系複合フィルムは、高分子膜で、隔離膜、固体電解質などの役割を果たし、通気度は１００乃至２０，０００秒/１００ｃｃである。
【００５２】
前記ｂ）の液体電解質は前記ａ）の多成分系複合フィルムと接触する時、支持層フィルム内部の気孔を満たしながらゲル化性高分子層を膨潤させ、ゲル化させる。液体電解質のイオン電導性向上のためにゲル化性高分子層の厚さを支持層フィルムの厚さより薄くする。これは高分子電解質の厚さに左右されるインピーダンス値を小さくするためである。
【００５３】
前記ｂ）の液体電解質はｉ）前記化学式２で示される塩がｉｉ）有機溶媒に溶解、解離している。
【００５４】
前記ｂ）ｉｉ）の有機溶媒は、プロピレンカーボネート（PC）、エチレンカーボネート（EC）、ジエチルカーボネート（DEC）、ジメチルカーボネート（DMC）、ジプロピルカーボネート（DPC）、ジメチルスルホキシド、アセトニトリル、ジメトキシエタン、ジエトキシエタン、テトラヒドロフラン、Ｎ−メチル−２−ピロリドン（NMP）、及びエチルメチルカーボネート（EMC）からなる群より１種以上選択されるのが好ましい。
【００５５】
このような本発明の高分子電解質システムは、スーパーコンデンサー（super capacitor）、ウルトラコンデンサー（ultra capacitor）、２次電池、１次電池、燃料電池、各種センサー、電気分解装置、電気化学的反応器などの様々な電気化学素子に適用できる。
【００５６】
以下の実施例、及び比較例を通じて本発明をさらに詳細に説明する。但し、実施例は本発明を例示するためのものであって、これらだけに限定されるわけではない。
【００５７】
[実施例]
実施例１
支持層フィルムとして高結晶性ポリプロピレンを、ゲル化性高分子層としてフッ化ポリビニリデン−三フッ化塩化エチレン共重合体３２００８（ソルベイポリマー（Solvay Polymer）社製造）を使用して次のような過程で高分子電解質用多成分系複合フィルムを製造した。
【００５８】
（フィルム前駆体の製造）
支持層として用いられるフィルム前駆体成分として溶融指数（melt index）２．０ｇ／１０分、密度０．９１ｇ／ｃｃ、ＤＳＣで測定された溶融温度１６６．５℃、結晶化温度１１６．５℃、結晶化度５７％、Ｃ13ＮＭＲで測定されたアイソタクチシティ９８％、キシレンで溶かした後、測定されたアタクチック比率約２％である高結晶性ポリプロピレンを用い、高結晶性ポリプロピレンをＴ−ダイが設けてある一軸押出機（single screw extruder）及び巻取り装置（take-up device）を利用して支持層フィルムを製造した。この時の押出温度は２２０℃、巻取り装置の冷却ロール温度は８０℃、巻取り速度は２０ｍ／分であり、巻取り比は６０であった。
前記で製造されたフィルム前駆体を乾燥オーブンで１５０℃の温度で１時間アニーリングした。
【００５９】
（塗布）
アニーリング後、前記３２００８を、アセトンを溶媒として溶解した溶液をアニーリングが終わったフィルム前駆体上にディップコーティング方式で両面に塗布した。この時、塗布は大気中で６０％程度の相対湿度を維持する条件で行い、同一な湿度条件でアセトンを蒸発させた。
【００６０】
（延伸）
塗布が終わった後、フィルムを常温で当初の長さに対して５０％の延伸倍率で１軸低温延伸し、再びフィルムを１４０℃の温度で１００％の延伸倍率で高温１軸延伸した。
【００６１】
（熱固定）
高温延伸後、１４０℃の温度で張力を受けた状態で１０分間熱固定をした後、冷却して多成分系複合フィルムを製造し、製造された多成分系複合フィルムの物性を測定してその結果を下記の表１に示した。
この時、通気度はＪＩＳＰ ８１１７方法、界面接着力はＪＩＳ Ｚ ０２３７方法によって測定し、気孔の大きさは、走査型電子顕微鏡（scanning electron microscopy）により、そして電解液の含浸速度は、体積比が４:６であるエチレンカーボネート:ジメチルカーボネート混合の電解液が面積２ｃｍ2のフィルム試料に完全に含浸される時間を測定した。
【００６２】
実施例２
（フィルム前駆体の製造）
前記実施例１と同一なフィルム前駆体を製造した。
【００６３】
（塗布）
ゲル化性高分子層としてフッ化ポリビニリデン−三フッ化塩化エチレン共重合体３２００８（ソルベイポリマー（Solvay Polymer）社製造）をアセトン溶媒に溶かした溶液を離型紙上にディップコーティング方式で両面に塗布させた。この時、塗布は大気中で６０％程度の相対湿度を維持する条件で行い、同一な湿度条件でアセトンを蒸発させた。
【００６４】
（熱融着）
前記で乾燥されたゲル化性高分子層２枚を離型紙から剥離し、この高分子層を前記フィルム前駆体の両面に位置させた後、１４０℃温度の加熱ラミネータを通過させてフィルム前駆体とゲル化性高分子層を熱融着した。
【００６５】
（延伸）
前記ゲル化性高分子層がフィルム前駆体の両面に熱融着されたフィルムを常温で当初の長さに対して５０％の延伸倍率で１軸延伸し、再びフィルムを１４０℃の温度で１００％の延伸倍率で高温１軸延伸した。
【００６６】
（熱固定）
高温延伸の後、１４０℃の温度で張力を受けた状態で１０分間熱固定した後、冷却して多成分系複合フィルムを製造し、製造された多成分系複合フィルムの物性を測定した結果、実施例１の多成分系複合フィルムと同一な物性を示した。
【００６７】
実施例３
（イオンビーム照射工程を経た高結晶性ポリプロピレン/フッ化ポリビニリデン−三フッ化塩化エチレン共重合体で構成された高分子電解質用多成分系複合フィルムの製造）
ゲル化性高分子層溶液を塗布する前にフィルム前駆体にイオンビームを照射したことを除いては前記実施例１と同様な方法で高分子電解質用多成分系複合フィルムを製造した。前記実施例１と同様な方法で製造されたフィルム前駆体を１０-5乃至１０-6ｔｏｒｒに維持させた真空槽に投入した後、アルゴン陽イオン（Ar+）を、イオン銃を利用してフィルム前駆体の両面に照射しながら同時にフィルム周囲に反応性ガス（酸素）の注入量を４ｍｌ/分にして、反応性ガス注入器によって注入し表面処理を行った。この時、イオンビームのエネルギーは０．５ｋｅＶ、イオン照射量は１０16ｉｏｎｓ/ｃｍ2であった。
イオンビーム照射工程が終わった後、前記実施例１と同様な方法で高分子電解質用多成分系複合フィルムを測定し、その結果製造した。製造された高分子電解質用多成分系複合フィルムの多様な物性を測定し、その結果を下記の表１に示した。
下記の表１を見てみると、実施例１と同様に実施例２の場合にも支持層及びゲル化性高分子層の双方に気孔が形成されており、高い透過度を示すことが観察でき、特に支持層とゲル化性高分子層の間の界面接着力が大きく改善されていて、電解液含浸速度も大きく改善されたことが分かる。
【００６８】
実施例４
（高密度ポリエチレン/フッ化ポリビニリデン−三フッ化塩化エチレン共重合体で構成された高分子電解質用多成分系複合フィルムの製造）
支持層として高結晶性ポリプロピレンの代りに高密度ポリエチレンを使用したことを除いては前記実施例１と同様な方法で多成分系複合フィルムを製造した。用いられた高密度ポリエチレンは溶融指数０．３ｇ／１０分、密度０．９６４ｇ／ｃｃであった。フィルム前駆体は前記実施例１と同様な方法で製造した。この時、押出温度は２００℃、巻取り装置の冷却ロール温度は８０℃、巻取り速度は３０ｍ/分、巻取り比は８０であった。製造されたフィルム前駆体を乾燥オーブンで１２５℃で１時間アニーリングした。アニーリングの後、実施例１と同様な方法でゲル化性高分子溶液をフィルム前駆体両面に塗布した。塗布が終わった後、常温で当初の長さに対して５０％の延伸倍率で１軸延伸し、その後、引続き１２０℃で５０％の延伸倍率で高温１軸延伸した。高温延伸後、１２０℃で張力を受けた状態で１０分間熱固定した後、冷却して多成分系複合フィルムを製造した。製造された高分子電解質用多成分系複合フィルムの多様な物性を下記の表１に示した。
【００６９】
下記の表１を見てみると、実施例１と同じく支持層及びゲル化性高分子層に共に気孔が形成されていて、高い透過度を示すことが分かり、支持層とゲル化性高分子層の間の界面接着力及び電解液含浸速度も改善されたことが分かる。
【００７０】
比較例１
各々の実施例で製造された高分子電解質と物性を比較するために、多孔質支持層フィルム上にゲル化性高分子層溶液を塗布する従来の方式によって高分子電解質を製造した。
支持層フィルムである微細気孔膜にはポリプロピレン単独で製造された製品である米国セラニズ（Celanese）社のセルガード２４００（Celanese2400）を用い、ゲル化性高分子層は前記実施例１と同一に前記３２００８を使用した。ゲル化性高分子層溶液を製造した後、気孔を有している前記セルガード２４００上にゲル化性高分子層溶液を塗布して乾燥した後、多層フィルムを製造して実施例１と同様な方法で物性を測定しその物性値を下記の表１に示した。
【００７１】
【表１】

Figure 0003885100
【００７２】
前記表１に示したように、比較例１の多層フィルムの場合、ゲル化性高分子層薄膜には微細気孔が観察されないのに反し、本発明の方法で製造された実施例１の多成分系複合フィルムは支持層フィルムの他にゲル化性高分子層にも微細気孔が形成されていることが見られ、これによって通気度が顕著に改善されたことが分かった。また、実施例１の場合、比較例１のフィルムより支持層フィルムとゲル化性高分子層の間の界面接着力、及び電解液含浸速度が向上したことが分かった。
【００７３】
実施例５
実施例１で製造された多成分系複合フィルムを１Ｍ ＬｉＰＦ6塩が含まれている有機電解液（ＥＣ/ＥＭＣの体積比は１:２）に浸漬させた後、ＳＵＳ電極を作業電極としてＬｉ金属を相手方電極とするＬｉ/多成分系複合分離膜/ＳＵＳのセルを構成した後、線状領域電解電量（Linear Sweep Voltametry）を常温の３乃至６Ｖ領域で１ｍＶ/ｓｅｃの速度で測定した。
【００７４】
図２は測定結果を示したグラフで、５Ｖ以下の電位では製造された複合フィルムが電気化学的に安定であるので高分子電解質として使用可能であることが確認できた。
【００７５】
従来の高分子電解質用多層フィルムの場合、通気度が殆ど測定できない程度の低い透過特性を示すのに反し、本発明によって製造された高分子電解質用多成分系複合フィルムは通気度が５００乃至６００ｓｅｃ/１００ｃｃを示すことによって、微細気孔を有する支持層以外にゲル化性高分子層にも気孔が形成されていることが分かる。
【００７６】
【発明の効果】
本発明によって製造された多成分系複合フィルムのゲル化性高分子層は従来のフィルムと同様に緻密な構造形態を有しており、加工条件によって気孔を形成することができ、また、その気孔の大きさが調節できて従来の多層フィルムに比べて顕著に改善された透過特性を示す。また、改善された透過特性以外に外郭層に存在するゲル化性高分子層の特性発現もやはり可能になる。つまり、本発明によって製造された高分子電解質用多成分系複合フィルムはその支持層が従来の乾式法工程を利用して製造された微細気孔分離膜と同一な物性を有し、ゲル化性高分子層はその工程条件によって多様に変化した形態を有する。
【００７７】
また、従来の高分子電解質用多層フィルムの場合、７５ｇfの界面接着力を示すのに対し、本発明によって製造された高分子電解質用多成分系複合分離フィルムの場合、１５０乃至２５０ｇfの界面接着力を示す。つまり、本発明の製造段階の一つである延伸工程中で高温を使用する高温延伸及び熱固定段階が存在するが、このような高温での工程を通じて支持層とゲル化性高分子層の間の高分子鎖の相互結合が増大して支持層とゲル化性高分子層の間の界面接着力が増加すると考えられる。このような界面接着力はイオンビーム照射工程を経る場合にさらに向上できる。また、このような界面接着力向上及び既に言及した形態変化によって電解液含浸速度も大きく改善できる。
【００７８】
電解質の含浸量が増加すれば電解質の漏出を減少させることができるので、電池が安定化する。また、含浸量が増加するために電解質の漏出量が減少するから、サイクル寿命特性は充放電をくり返しても低下しない。
【００７９】
本発明の多成分系複合フィルムは、電気化学的安定性、電極との接着性、電解液含浸性及び安定性などが満足されながらも可塑剤を抽出したり除去したりする工程が不要であり、イオンの伝導度と機械的物性を同時に満足する多成分系複合フィルムであって、高分子電解質システムや電気化学素子、及び分離膜に用いられる。
【図面の簡単な説明】
【図１】 ゲル化性高分子層１２が支持層フィルム１１の両面に位置する多成分系複合フィルムの構造を示す図面であって、ゲル化性高分子層１２を支持層フィルム１１上に塗布した後、延伸及び熱固定の過程を経て二つの層間の界面１３が不明確となったことを示す断面図である。
【図２】 実施例２のＬｉ/多成分系複合フィルム（ゲル化性高分子層はフッ化ポリビニリデン−三フッ化塩化エチレン、支持層フィルムはpolypropylene）/ＳＵＳ構造のセルでLinear Sweep Voltametryを実施した結果を示すグラフである。
【符号の説明】
１１ 支持層フィルム
１２ ゲル化性高分子層
１３ 界面[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a multicomponent composite film and a method for producing the same, and more particularly to a multicomponent composite film that can be used as a polymer electrolyte for an electrochemical device, a method for producing the same, and a polymer electrolyte system to which the multicomponent composite film is applied.
[0002]
[Prior art]
Recently, interest in energy conservation technology has increased. For example, energy conservation technology is important in mobile phones, camcorders, notebook computers, electric vehicles, etc., so research and development on batteries, which are a kind of energy conservation means, are actively conducted, and among them, charging / discharging Possible secondary batteries are the focus of interest. In recent years, research on developing new electrodes and polymer electrolytes has been continuously carried out in order to improve the performance of battery development and increase the yield and economy of the battery manufacturing process. In particular, the development of new polymer electrolytes is of great interest from the perspective of creating new high performance batteries with improved safety.
[0003]
Electrolytes can be broadly classified into two types: liquid electrolytes and solid electrolytes. The liquid electrolyte is one in which a salt is dissolved and dissociated in an organic solvent and can conduct ions between the positive electrode and the negative electrode, and has an advantage of high ion conductivity. However, the liquid electrolyte is actually used in a battery together with a polymer separation membrane. For example, a microporous structure is formed inside a polymer film such as polyolefin, and the pores are filled with the liquid electrolyte and have ionic conductivity. Like that. Although there are differences depending on the porosity of the polymer separation membrane and its structure, in this case, the ion conductivity is about 1 mS / cm. However, when the liquid electrolyte existing inside the pores is in a non-normal state due to the high fluidity, the liquid electrolyte may easily bleed or leak out of the polymer separation membrane. In addition, there is a disadvantage that the battery must always be configured with simple contact since the interface between the electrodes is not bonded in forming the interface. The advantage is that the polymer separation membrane itself has a high degree of crystallinity, so it has excellent mechanical strength and is never excessively swollen or decomposed due to little influence from the liquid electrolyte. That is.
[0004]
On the other hand, in the case of a solid electrolyte, there is a disadvantage that the ion conductivity at room temperature is not sufficient for realizing the performance of the battery. In order to solve this problem, a gelled polymer electrolyte in which a solid electrolyte is impregnated with a liquid electrolyte in which a salt is dissolved in an organic solvent is used. For example, Bellcore There is a hybrid type (US Pat. No. 5,418,091) developed by the company. However, the gel type polymer electrolyte has a disadvantage that the mechanical strength is low and has a problem in assembling the battery. The gel type polymer electrolyte maintains the insulation between the electrodes and has a high gel type due to the mechanical strength required in the process. The thickness of the molecular electrolyte must generally exceed 50 μm, but the thickness of such a polyelectrolyte induces abnormal problems such as an increase in thickness due to excessive swelling of the gel polymer, and the volume This causes problems such as a decrease in energy density due to an increase in energy consumption. In addition to the problems mentioned above, the use of low molecular weight plasticizers, which are environmentally problematic, and the burden of the extraction process are major obstacles in mass production.
[0005]
The conditions that the polymer electrolyte must have include electrochemical stability and thermal and chemical stability within the operating voltage range. The ion conductivity at room temperature must exceed 1 mS / cm for battery operation, and the impregnation and chemical resistance must be better than in the case of a non-aqueous electrolyte. Further, in order to reduce the interfacial resistance with the electrode when assembling the battery, it must have adhesiveness, and sufficient mechanical strength required during the assembling process is also required. However, in general, when the conductivity of ions is improved, mechanical properties are deteriorated, and when the mechanical properties are improved, ion conductivity is decreased.
[0006]
In order to solve the above-mentioned problems of ionic conductivity and mechanical properties conflicting, it was proposed to use a porous polymer layer and a gelled polymer multilayer film as a battery separation membrane. (US Pat. Nos. 5,639,573, 5,716,421, 5,631,103, 5,849,433, European Patent Publication No. 0933824 A2). Here, the porous polymer is a substance that absorbs the liquid electrolyte limitedly in the pores and hardly swells. For example, polyethylene (polyethylene), polypropylene (polypropylene), polytetrafluoroethylene (polytetrafluoroethylene) , Polyethylene terephthalate, polybutyleneterephthalate, polyethylenenaphthalate, etc. and a combination of these films. A gelling polymer means a polymer that gels and swells when it comes into contact with a liquid electrolyte, such as polyvinylidene fluoride, polyurethane, polyethylene oxide, and polyacrylonitrile. , Polymethylmethacrylate, polycrylamide, polyvinylacetate, polyvinylpyrrolidinone, polytetracthylene glycol diacrylate and copolymers of such polymers it can.
[0007]
[Problems to be solved by the invention]
Such a structure can improve the mechanical properties, but is lower than the ionic conductivity of the porous polymer layer and the liquid electrolyte impregnated in the porous polymer layer due to the antiionic conductivity of the gelling polymer. It will have ionic conductivity. Therefore, the use of a low molecular weight plasticizer such as dibutyl phthalate is required to improve ion conductivity (US Pat. No. 5,631,103, US Pat. No. 5,849,433). issue). However, the use of the plasticizer causes various problems as described above. Further, in the case of a multilayer structure film manufactured by such a method, the gelled polymer layer present on the outer surface of the porous polymer layer has a dense structure without pores, and has a large ion conduction resistance. There is a disadvantage that the interfacial adhesion between the layers is weakened.
[0008]
In consideration of the problems of the prior art, the present invention eliminates the step of extracting or removing the plasticizer while satisfying the electrochemical stability, adhesion to the electrode, electrolyte solution impregnation property and stability. It is an object of the present invention to provide a multicomponent composite film that is manufactured and satisfies the ionic conductivity and mechanical properties at the same time, a manufacturing method thereof, and a polymer electrolyte system using the multicomponent composite film.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a multicomponent composite film,
a) a polymeric support layer film; and
b) A porous gellable polymer layer formed on one or both sides of the film
The support layer film as component a) and the porous gelling polymer layer as component b) are integrated without an interface.
[0010]
Further, the present invention provides a method for producing the multicomponent composite film,
a) producing a polymeric support layer film;
b) dissolving the gelling polymer in a solvent to produce a gelling polymer solution;
c) applying the gelling polymer solution of step b) to one or both sides of the support layer film of step a) to form a gelling polymer layer to produce a multilayer film; and
d) A step of heat setting after stretching the multilayer film of step c).
There is provided a method for producing a multi-component composite film in which a support layer film containing a gel and a gelling polymer layer are integrated without an interface.
[0011]
In addition, the present invention provides a polymer electrolyte system using the multi-component composite film as a separation membrane, and an electrochemical device including the polymer electrolyte system.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0013]
The present invention relates to a porous film produced by applying a gelling polymer liquid on a conventional microporous film having pores of a certain size, a multilayer film for polymer electrolyte having a gelling polymer substance having an interface, In contrast, a gelling polymer material is coated on a general polymer film having no pores to form a gelling polymer layer on the polymer film, and then stretched at a high temperature to form pores. As a result, an integrated multi-component composite film is produced without forming an interface between the polymer film and the gelling polymer layer.
[0014]
In this way, integration without forming an interface between the polymer film (polymer support layer) and the gelling polymer substance (porous gelling polymer layer) is an interdiffusion at a high temperature in the stretching process. (Inter-diffusion), the mutual bond increases between the polymer of the support layer and the gelling polymer layer, and they are integrated to the extent that they are difficult to separate. Specifically, when the interfacial adhesive force of the multi-component composite film of the present invention is measured by the method of JIS Z 0237, it has an interfacial adhesive force of at least 100 gf, preferably at least 150 gf.
[0015]
In addition, a polymer electrolyte system for an electrochemical element to which the multicomponent composite film is applied is realized by impregnating such a multicomponent composite film with a liquid electrolyte containing a salt and an organic solvent. In particular, such a polymer electrolyte system has a gelling polymer substance alone or a gelling polymer and a salt that are applied to one or both sides of a support layer in an electrochemical element such as a battery. The formed polymer-salt complex can be used as an electrolyte.
[0016]
Hereinafter, the configuration of the multicomponent composite film will be described.
[0017]
The support layer film of a) is a high density polyethylene, a low density polyethylene, a linear low density polyethylene, a polypropylene, a high crystalline polypropylene. polypropylene), polyethylene-propylene copolymer, polyethylene-butylene copolymer, polyethylene-hexene copolymer, polyethylene-octene copolymer (polyethylene) -octene copolymer), polystyrene-butylene-styrene copolymer, polystyrene-ethylene-butylene-styrene copolymer, polystyrene, polyphenylene oxide ( Polyphenylene oxide, Polysulfone, Polycarbonate, Polyester, Polyamide, Polyurethane, Polyacrylate, Polyvinylidene chloride, Polyvinylidene fluoride 1 or more selected from the group consisting of polysiloxane, polyolefin ionomer, polymethyl pentene, hydrogenated oligocyclopentadiene (HOCP), and copolymers or derivatives thereof Preferably, the polymer to be produced is produced in a blended or laminated form.
[0018]
In particular, the high crystalline polypropylene has a density of 0.905 g / cc or higher, a melting temperature of 164 ° C. or higher, a crystallization temperature of 125 ° C. or higher, a crystallinity of 50% or higher, an isotacticity (or pentad ratio) of 96% or higher, and an atactic. It is preferable that one or more conditions are satisfied within a ratio of less than 5%.
[0019]
The material of the gelling polymer layer b) is selected depending on the use of the multi-component composite film. Generally, polyvinylidene fluoride, polyvinylidene fluoride-polyethyleneidene fluoride-polyvinylidene fluoride- chlorotrifluoroethylene copolymer, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, polypropylene oxide, polybutylene oxide, polyurethane, poly Acrylonitrile, polyacrylate, polymethyl methacrylate, polyacrylic acid, polyamide, polyacrylamide, polyvinyl acetate polyvinyl acetate, polyvinylpyrrolidone, polytetraethylene glycol diacrylate, polysulfone, polyphenylene oxide, polycarbonate, polyester, polyvinylidene chloride ), Polysiloxane, polyolefin ionomer, and copolymers or derivatives thereof.
[0020]
The gelling polymer layer preferably contains a polymer-lithium salt complex in order to improve the ion transference number due to the fixation of anions. Accordingly, LiSCN and LiClO are materials that have a higher melting energy than lithium lattice energy that is involved in forming a coordinate bond between lithium ions and an element capable of donating electrons.Four, LiCFThreeSOThree, LiAsF6, LiN (CFThreeSO2)2, And LiBFFourA lithium salt selected from at least one selected from the group consisting of:
[0021]
In addition, the gelling polymer layer is made of silica (SiO 2) to further improve the ion transition number.2), Titanium oxide (TiO2), Alumina (Al2OThree), Magnesium oxide (MgO), and barium oxide (B2OThree1) or more porous inorganic particles selected from the group consisting of:
[0022]
Hereinafter, a method for producing the multicomponent composite film will be described.
[0023]
The multi-component composite film of the present invention is formed by forming a gelling polymer layer on one or both sides of the above-mentioned support layer film of various materials with a solution in which the gelling polymer described above is dissolved in a solvent. The film is stretched to form pores in the film, so that an interface is not formed between the polymer film and the gelling polymer substance, and the film is integrated. At this time, pores are formed in the gelling polymer layer in addition to the support layer film.
[0024]
The support layer film in step a) is obtained by extruding the above-described polymer with an extruder equipped with a T-die or a tubular die, and then crystallinity and elastic recovery rate. In order to increase the temperature, it is preferable to manufacture by annealing in a drying oven at room temperature to the maximum melting point of the maximum polymer.
[0025]
Further, such a support layer film can be irradiated with an ion beam under introduction of a reactive gas in order to further improve the interfacial adhesive force with the gelling polymer layer. Such ion beam irradiation is a kind of surface modification method, and can be applied to all before or after annealing of the film, and the feasibility of the implementation is determined by the physical properties of the final multi-component composite film.
[0026]
The ion beam irradiation process with the reactive gas introduced will be described in detail.-1Thru 10-6After the support layer film 11 is put into a vacuum chamber maintained at a high vacuum of about torr, electrons, hydrogen, helium, oxygen, nitrogen, carbon dioxide, air, fluoride, neon, argon, krypton, N20.01 to 10 by injecting one or more ion generating gases selected from the group consisting of O6After producing particles having an energy of about keV, one side or both sides of the support layer film are irradiated with the particles having energy while changing the ion beam current. When such an ion beam is irradiated, the irradiation amount of ion particles is 10FiveThru 1020ions / cm2Is preferred. Simultaneously with ion beam irradiation, helium, hydrogen, oxygen, nitrogen, ammonia, carbon monoxide, carbon dioxide, chlorofluoro, methane, and N around the film2One or more reactive gases selected from the group consisting of O are injected at a rate of 0.5 to 20 ml / min with a reactive gas injector to modify the surface.
[0027]
In the multi-component composite film of the present invention, a gelling polymer layer is formed on one or both sides of the support layer film using a gelling polymer solution. This gelling polymer solution is produced by dissolving the above-described gelling polymer in a solvent.
[0028]
The solvent is 1-methyl-2-pyrrolidone (NMP), acetone, ethanol, n-propanol, n-butanol, n-hexane, cyclohexanol, acetic acid, ethyl acetate, diethyl ether, dimethylformamide (DMF), dimethylacetamide ( DMAc), a single solvent or a mixed solvent selected from the group consisting of dioxane, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), cyclohexane, benzene, toluene, xylene, and water. The concentration and application conditions of such a gelling polymer solution can vary depending on the substance used, but the concentration is particularly preferably 0.01 to 90% by weight. Further, when such a gelling polymer solution is produced, the above-described lithium salt, inorganic porous particles, or a mixture thereof may be added together with the gelling polymer.
[0029]
The gelling polymer layer can be formed by two methods. One method is a method in which the gelling polymer solution is applied to a support layer film and then dried under suitable conditions to form a layer. In another method, a gelling polymer solution is coated on a release paper or a release film and then dried under the same conditions as in the first method to produce a film form. In this method, after peeling and positioning on the support layer film, heat bonding is performed with a laminator or the like. The thermal bonding at this time can be easily bonded by selecting the material of the support layer film and the heat fusion temperature of the gelling polymer. That is, it is performed at room temperature or a temperature of the melting point of the support layer or the gelling polymer layer.
[0030]
The specific manufacturing process of the process is as follows.
[0031]
After applying the gelling polymer solution to the support layer film, drying it under appropriate conditions to form a thin film, and then stretching the first method,
a) introducing a polymer used as a support layer into an extruder to produce a film precursor;
b) annealing the prepared film precursor at a temperature below the melting point of the polymer;
c) irradiating one or both surfaces of the annealed film precursor with an ion beam with the aid of a reactive gas when necessary;
d) applying a gelling polymer solution to one or both sides of the film precursor irradiated with the ion beam;
e) drying the polymer solution applied to one or both surfaces of the film precursor;
f) a step of low-temperature stretching the film precursor from which the polymer solution has been dried at a temperature below room temperature;
g) stretching the low temperature stretched film precursor at a temperature below the melting point of the polymer; and
h) heat-setting the high-temperature stretched film precursor in a tensioned state at a temperature below the melting point of the polymer;
including.
[0032]
Other methods of stretching after applying the gelling polymer solution on the release paper or release film and thermally bonding it to the support layer film are as follows:
a) introducing a polymer used as a support layer into an extruder to produce a film precursor;
b) annealing the prepared film precursor at a temperature below the melting point of the polymer; c) irradiating one or both surfaces of the annealed film precursor with an ion beam with the aid of a reactive gas when necessary. Stage;
d) applying a gelling polymer solution onto a release paper or release film;
e) drying the polymer solution coated on the release film;
f) a step of thermally bonding to one or both sides of the film precursor after peeling the dried gellable polymer layer film from the release film;
g) a step of subjecting the film precursor, to which the gelling polymer film is thermally bonded, to low temperature stretching at a temperature of room temperature or lower;
h) high temperature stretching the low temperature stretched film precursor at a temperature below the melting point of the polymer; and
i) Step of heat-setting the high-temperature stretched film precursor in a state where tension is applied at a temperature not higher than the melting point of the polymer.
including.
[0033]
The gelling polymer solution may be applied directly to the support layer film or to the release paper or release film by dip coating, spray coating, spin coating, or die coating. (Die coating), roll coating (Roll coating) and the like can be carried out, and the method is not particularly limited. The thickness of the coating varies depending on the use of the final multicomponent composite film, but if the thickness of the support layer film is 1 to 50 μm, the thickness of the gelling polymer layer is 0.01 to 25 μm after drying. It is preferable to do so.
[0034]
Such coating can be performed before or after film annealing, or before and after, and depending on the properties of the multi-component composite film, an ion beam irradiation process can be performed with the aid of a reactive gas before the coating process.
[0035]
Drying of the applied gelling polymer solution was surrounded by a gas selected from the group consisting of nitrogen, oxygen, carbon dioxide, and air at a temperature equal to or lower than the solvent saturation vapor pressure of the gelling polymer solution. It is preferably carried out under an atmosphere, and the humidity is preferably carried out under conditions of 1 to 100% relative humidity.
[0036]
The multicomponent composite film of the present invention has a gelling polymer layer coated on one or both sides of the support layer film and the support layer film after the gelling polymer layer is formed on one or both sides of the support layer film. Pore is formed in
[0037]
In general, methods for forming pores in a polymer film include a phase transition method and a dry method. The phase transition method is a method of forming pores by creating a polymer solution and then causing a phase transition between the polymer and the solvent by appropriately using temperature or a non-solvent. Characteristics are determined. The dry method is a method in which the polymer crystal part is oriented in a certain direction and then a relatively weak amorphous part is ruptured by cold drawing to form pores, depending on the uniform orientation and degree of the crystal part. The characteristics of the manufactured film are determined.
[0038]
In the present invention, in order to form appropriate pores, the gelling polymer layer is formed on one side or both sides of the support layer film and then stretched. At this time, the pore size and distribution of the support layer and the gelling polymer layer are different from each other. Explaining this, the support layer has pores formed by stretching after the crystal structure of the film precursor is oriented in a certain direction in the manufacturing process. On the other hand, pores are formed in the gelable polymer layer by the phase transition method and the dry method. In this case, the gelable polymer layer has a phase transition between the gelable polymer and the solvent. As a result, fine pores or fine cracks are generated, and the diameter or size of the pores is increased by the stretching treatment. In particular, the gelling polymer layer can be formed in various forms such as a dense structure, fine cracks or fine pores before stretching depending on the phase transition conditions, and the degree of formation can be adjusted.
[0039]
Therefore, the pores of the support layer and the gelling polymer layer have different pore sizes and distributions due to differences in the manufacturing process.
[0040]
The stretching includes a low temperature stretching step and a high temperature stretching step.
[0041]
The low-temperature stretching is performed by uniaxially stretching a multilayer film having a gelling polymer layer formed on one or both sides of a support layer film under a temperature condition of 0 to 50 ° C. using a roll or other stretching machine. A fine crack is generated in the support layer to enlarge the size of the pores already formed in the gelling polymer layer 12.
[0042]
The high-temperature stretching is performed by uniaxially forming a microcrack formed by the low-temperature stretching using a roll or other stretching machine under a temperature condition of 50 ° C. to the maximum supporting layer or the melting point of the polymer of the gelling polymer layer. Alternatively, biaxial stretching is performed to form fine pores having a desired size, and mechanical properties are imparted to the film through such high-temperature stretching.
[0043]
The multilayer film stretched at a low temperature and a high temperature as described above is heat-set after stretching. Such heat fixation is carried out for a certain period of time of 10 seconds to 1 hour as it is under tension in the temperature range from 50 ° C. to the maximum support layer or the melting point of the polymer of the gelling polymer layer. Through the process, a multi-component composite film including a support layer film and a gelling polymer layer is finally produced.
[0044]
In the multi-component composite film of the present invention, the inter-diffusion of the polymer chain between the support layer film and the gelling polymer layer is increased through the high-temperature stretching and heat setting steps, and the support layer film The interfacial adhesive force between the gel layer and the gelling polymer layer is increased, whereby the interface between the support layer and the gelling polymer layer is unclear and integrated. In particular, as described above, when the support layer film is irradiated with an ion beam while introducing a reactive gas, the adhesive force at such an interface further increases.
[0045]
The multi-component composite film after passing through the high-temperature stretching and heat setting steps has a pore size of 0.001 to 10 μm and a thickness of 1 to 50 μm in the support layer film, and one or both sides of the support layer film. The porous gelling polymer layer located in the layer has a maximum pore size of 10 μm and a thickness of 0.01 to 25 μm, and is preferably used for a polymer electrolyte system or an electrochemical device. It is.
[0046]
FIG. 1 is an example of the structure of such a multi-component composite film of the present invention, in which a gelling polymer layer 12 is located on both sides of a support layer film 11. At this time, the support layer film 11 and the gelling polymer are formed by the stretching and heat setting processes performed after the gelling polymer layer 12 is applied to the surface of the support layer film 11 in the multicomponent composite film manufacturing process. It shows that the interface 13 between the layers 12 has become unclear. In addition, a multi-component composite film integrated without such an interface has excellent ionic conductivity and electrochemical stability.
[0047]
In the method for producing a multi-component composite film of the present invention, each step may be omitted in some steps or additional steps may be added depending on the desired end use. Can change.
[0048]
The multicomponent composite film of the present invention can be used in various separation membranes such as microfiltration membranes, ultrafiltration membranes, gas separations, pervaporation membranes, reverse It can be used as a reverse osmosis membrane or a separation membrane for electrochemical devices. In particular, in a polymer electrolyte system, electrochemical stability, adhesion to electrodes, electrolyte solution impregnation, and stability can be imparted.
[0049]
The present invention
a) i) a porous support layer film; and
ii) The above-mentioned i) includes a porous gelling polymer layer formed on one side or both sides of the supporting layer film, and the supporting layer film of i) and the porous gelling polymer layer of ii) are integrated without any interface. A separation membrane of a multicomponent composite film that has been converted; and
b) i) a salt of formula 2 below; and
ii) Organic solvent
Liquid electrolyte containing
A polyelectrolyte system is provided.
[0050]
[Chemical formula 2]
A+B-
In the above formula,
A+Li+, Na+, And K+At least one selected from the group consisting of alkali metal cations and derivatives thereof,
B-Is PF6 -, BFFour -, Cl-, Br-, I-, AsF6 -, CHThreeCO2 -, CFThreeSOThree -, N (CHThreeSO2)2 -, And C (CHThreeSO2)Three -One or more selected from the group consisting of:
[0051]
The multi-component composite film a) is a polymer film, and serves as a separator, a solid electrolyte, etc., and has an air permeability of 100 to 20,000 seconds / 100 cc.
[0052]
When the liquid electrolyte of b) comes into contact with the multicomponent composite film of a), the gelling polymer layer is swollen and gelled while filling the pores inside the support layer film. In order to improve the ionic conductivity of the liquid electrolyte, the gelling polymer layer is made thinner than the support layer film. This is to reduce the impedance value that depends on the thickness of the polymer electrolyte.
[0053]
In the liquid electrolyte of b), i) the salt represented by the chemical formula 2 is dissolved and dissociated in ii) an organic solvent.
[0054]
The organic solvent of b) ii) is propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, di It is preferable that at least one selected from the group consisting of ethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), and ethyl methyl carbonate (EMC).
[0055]
Such a polymer electrolyte system of the present invention includes a super capacitor, an ultra capacitor, a secondary battery, a primary battery, a fuel cell, various sensors, an electrolysis apparatus, an electrochemical reactor, and the like. It can be applied to various electrochemical devices.
[0056]
The present invention will be described in more detail through the following examples and comparative examples. However, the examples are for illustrating the present invention and are not limited thereto.
[0057]
[Example]
Example 1
Using highly crystalline polypropylene as the support layer film and polyvinylidene fluoride-trifluoroethylene chloride copolymer 32008 (manufactured by Solvay Polymer) as the gelling polymer layer, the following process A multi-component composite film for polymer electrolyte was produced.
[0058]
(Production of film precursor)
As a film precursor component used as a support layer, a melt index of 2.0 g / 10 min, a density of 0.91 g / cc, a melting temperature measured by DSC of 166.5 ° C., a crystallization temperature of 116.5 ° C., Crystallinity 57%, C13A single screw extruder in which a high crystallinity polypropylene having a measured atactic ratio of about 2% is dissolved in 98% isotacticity measured by NMR and xylene, and a high crystalline polypropylene is provided with a T-die ( A support layer film was produced using a single screw extruder and a take-up device. At this time, the extrusion temperature was 220 ° C., the cooling roll temperature of the winding device was 80 ° C., the winding speed was 20 m / min, and the winding ratio was 60.
The film precursor prepared above was annealed in a drying oven at a temperature of 150 ° C. for 1 hour.
[0059]
(Application)
After annealing, the 32008 was applied on both sides by a dip coating method on the film precursor after the annealing with a solution of acetone as a solvent. At this time, the application was performed under the condition of maintaining a relative humidity of about 60% in the atmosphere, and acetone was evaporated under the same humidity condition.
[0060]
(Stretching)
After coating, the film was uniaxially cold stretched at a stretch ratio of 50% with respect to the original length at room temperature, and the film was stretched uniaxially at a stretch ratio of 100% at a temperature of 140 ° C. again.
[0061]
(Heat fixing)
After high-temperature stretching, heat-fixed for 10 minutes in a state of receiving a tension at a temperature of 140 ° C., and then cooled to produce a multi-component composite film. The physical properties of the produced multi-component composite film were measured and The results are shown in Table 1 below.
At this time, the air permeability was measured by the JISP 8117 method, the interfacial adhesion was measured by the JIS Z 0237 method, the pore size was measured by scanning electron microscopy, and the impregnation rate of the electrolyte was determined by the volume ratio. The electrolyte of 4: 6 ethylene carbonate: dimethyl carbonate is 2cm in area.2The time for complete impregnation of the film sample was measured.
[0062]
Example 2
(Production of film precursor)
The same film precursor as in Example 1 was manufactured.
[0063]
(Application)
As a gelling polymer layer, a solution prepared by dissolving polyvinylidene fluoride-trifluoroethylene chloride copolymer 32008 (manufactured by Solvay Polymer) in acetone solvent is applied to both sides by dip coating on release paper. I let you. At this time, the application was performed under the condition of maintaining a relative humidity of about 60% in the atmosphere, and acetone was evaporated under the same humidity condition.
[0064]
(Heat fusion)
The two gelling polymer layers dried above are peeled off from the release paper, and after the polymer layers are positioned on both sides of the film precursor, the film precursor is passed through a heating laminator at 140 ° C. And the gelling polymer layer were heat-sealed.
[0065]
(Stretching)
The film in which the gelling polymer layer is thermally fused on both sides of the film precursor is uniaxially stretched at a stretch ratio of 50% with respect to the original length at room temperature, and the film is again stretched at a temperature of 140 ° C. to 100. The film was uniaxially stretched at a high temperature at a stretch ratio of%.
[0066]
(Heat fixing)
After hot stretching, after heat fixing for 10 minutes in a state of receiving tension at a temperature of 140 ° C., cooling to produce a multi-component composite film, and as a result of measuring the physical properties of the produced multi-component composite film, The same physical properties as those of the multi-component composite film of Example 1 were exhibited.
[0067]
Example 3
(Manufacture of multi-component composite film for polymer electrolytes composed of highly crystalline polypropylene / polyvinylidene fluoride-ethylene trifluoride chloroethylene copolymer through ion beam irradiation process)
A multi-component composite film for polymer electrolyte was produced in the same manner as in Example 1 except that the film precursor was irradiated with an ion beam before applying the gelling polymer layer solution. A film precursor produced by the same method as in Example 1 was used.-FiveThru 10-6After putting into a vacuum chamber maintained at torr, an argon cation (Ar+) Is irradiated on both sides of the film precursor using an ion gun, and at the same time, the amount of reactive gas (oxygen) is 4 ml / min. It was. At this time, the energy of the ion beam is 0.5 keV, and the ion irradiation amount is 1016ions / cm2Met.
After the ion beam irradiation process was finished, the multicomponent composite film for polymer electrolyte was measured by the same method as in Example 1 and manufactured as a result. Various physical properties of the produced multi-component composite film for polymer electrolyte were measured, and the results are shown in Table 1 below.
Looking at Table 1 below, it is observed that in the case of Example 2 as well as in Example 1, pores are formed in both the support layer and the gelling polymer layer and show high permeability. In particular, it can be seen that the interfacial adhesive force between the support layer and the gelling polymer layer is greatly improved, and the electrolyte impregnation rate is also greatly improved.
[0068]
Example 4
(Manufacture of multicomponent composite films for polymer electrolytes composed of high density polyethylene / polyvinylidene fluoride-trifluoroethylene chloride copolymer)
A multicomponent composite film was produced in the same manner as in Example 1 except that high-density polyethylene was used in place of the highly crystalline polypropylene as the support layer. The high density polyethylene used had a melt index of 0.3 g / 10 min and a density of 0.964 g / cc. The film precursor was produced in the same manner as in Example 1. At this time, the extrusion temperature was 200 ° C., the cooling roll temperature of the winding device was 80 ° C., the winding speed was 30 m / min, and the winding ratio was 80. The produced film precursor was annealed in a drying oven at 125 ° C. for 1 hour. After annealing, a gelling polymer solution was applied to both sides of the film precursor in the same manner as in Example 1. After the coating was completed, the film was uniaxially stretched at a stretch ratio of 50% with respect to the original length at room temperature, and then stretched uniaxially at 120 ° C. at a stretch ratio of 50%. After stretching at high temperature, the film was heat-set for 10 minutes in a state of receiving a tension at 120 ° C., and then cooled to produce a multicomponent composite film. Various physical properties of the produced multi-component composite film for polymer electrolyte are shown in Table 1 below.
[0069]
Looking at Table 1 below, it can be seen that both the support layer and the gelling polymer layer have pores formed in the same manner as in Example 1 and show high permeability. It can be seen that the interfacial adhesion between the layers and the electrolyte impregnation rate were also improved.
[0070]
Comparative Example 1
In order to compare the properties with the polymer electrolytes produced in the respective examples, polymer electrolytes were produced by a conventional method in which a gelling polymer layer solution was applied onto a porous support layer film.
For the microporous membrane as the support layer film, Cellguard 2400 (Celanese 2400) of US Celanese Co., Ltd., which is a product made of polypropylene alone, was used. It was used. After preparing the gelling polymer layer solution, the gelling polymer layer solution was applied on the cell guard 2400 having pores and dried, and then a multilayer film was manufactured to obtain the same as in Example 1. The physical properties were measured by the method, and the physical property values are shown in Table 1 below.
[0071]
[Table 1]
Figure 0003885100
[0072]
As shown in Table 1, in the case of the multilayer film of Comparative Example 1, the multi-component of Example 1 produced by the method of the present invention was contrary to the fact that no fine pores were observed in the gelled polymer layer thin film. The system composite film was found to have fine pores formed in the gelling polymer layer in addition to the support layer film, and this proved that the air permeability was remarkably improved. Moreover, in the case of Example 1, it turned out that the interface adhesive force between a support layer film and a gelling polymer layer and the electrolyte solution impregnation rate improved from the film of the comparative example 1.
[0073]
Example 5
The multi-component composite film produced in Example 1 was replaced with 1M LiPF.6After immersing in an organic electrolyte containing salt (volume ratio of EC / EMC is 1: 2), Li / multicomponent composite separation membrane / SUS with SUS electrode as working electrode and Li metal as counter electrode After the above cell was constructed, the linear area sweep electric capacity (Linear Sweep Voltametry) was measured at a rate of 1 mV / sec in a 3 to 6 V region at room temperature.
[0074]
FIG. 2 is a graph showing the measurement results, and it was confirmed that the composite film produced was electrochemically stable at a potential of 5 V or less and could be used as a polymer electrolyte.
[0075]
In the case of the conventional multilayer film for polymer electrolyte, the multicomponent composite film for polymer electrolyte produced according to the present invention has an air permeability of 500 to 600 sec. By indicating / 100 cc, it can be seen that pores are formed not only in the support layer having fine pores but also in the gelling polymer layer.
[0076]
【The invention's effect】
The gelable polymer layer of the multi-component composite film produced according to the present invention has a dense structure form as in the conventional film, and can form pores depending on processing conditions. The size of the film can be adjusted, and the transmission characteristics are remarkably improved as compared with the conventional multilayer film. In addition to the improved permeation characteristics, it is also possible to develop the characteristics of the gelling polymer layer present in the outer layer. That is, the multi-component composite film for polymer electrolytes produced according to the present invention has the same physical properties as the microporous separation membrane produced by using the conventional dry process, and has a high gelling property. The molecular layer has various shapes that vary depending on the process conditions.
[0077]
In the case of a conventional multilayer film for polymer electrolyte, 75 gfIn the case of the multi-component composite separation film for polymer electrolyte produced according to the present invention, 150 to 250 gfThe interfacial adhesive strength of is shown. In other words, there is a high temperature drawing and heat setting step that uses a high temperature in the drawing process, which is one of the production steps of the present invention. Between the support layer and the gelling polymer layer through the high temperature process, It is considered that the mutual bond between the polymer chains increases and the interfacial adhesive force between the support layer and the gelling polymer layer increases. Such an interfacial adhesive force can be further improved when an ion beam irradiation process is performed. Also, the electrolyte solution impregnation rate can be greatly improved by the improvement of the interfacial adhesive force and the above-described change in form.
[0078]
If the amount of electrolyte impregnation increases, leakage of the electrolyte can be reduced, so that the battery is stabilized. In addition, since the amount of electrolyte leakage decreases due to an increase in the amount of impregnation, the cycle life characteristics do not deteriorate even if charging and discharging are repeated.
[0079]
The multi-component composite film of the present invention does not require a step of extracting or removing a plasticizer while satisfying electrochemical stability, adhesion to an electrode, electrolyte solution impregnation property and stability. A multi-component composite film that satisfies both ionic conductivity and mechanical properties at the same time, and is used for a polymer electrolyte system, an electrochemical device, and a separation membrane.
[Brief description of the drawings]
FIG. 1 is a view showing the structure of a multi-component composite film in which a gelling polymer layer 12 is located on both sides of a support layer film 11, and the gelling polymer layer 12 is applied on the support layer film 11; It is sectional drawing which shows that the interface 13 between two layers became indefinite after passing through the process of extending | stretching and heat setting.
2] Li / multicomponent composite film of Example 2 (gelling polymer layer is polyvinylidene fluoride-trifluoroethylene chloride, support layer film is polypropylene) / Linear Sweep Voltametry in SUS cell. It is a graph which shows the implemented result.
[Explanation of symbols]
11 Support layer film
12 Gelling polymer layer
13 Interface

Claims (19)

ａ） 高密度ポリエチレン、低密度ポリエチレン、線状低密度ポリエチレン、ポリプロピレン、高結晶性ポリプロピレン、ポリエチレン−プロピレン共重合体、ポリエチレン−ブチレン共重合体、ポリエチレン−ヘキセン共重合体、ポリエチレン−オクテン共重合体、ポリスチレン−ブチレン−スチレン共重合体、ポリスチレン−エチレン−ブチレン−スチレン共重合体、ポリスチレン、ポリフェニレンオキシド、ポリスルホン、ポリカーボネート、ポリウレタン、ポリアクリレート、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリシロキサン、ポリオレフィンアイオノマー、ポリメチルペンテン、水素添加オリゴシクロペンタジエン、及びこれらの共重合体または誘導体からなる群より１種以上選択される高分子支持層フィルムを製造する段階;
ｂ） ポリフッ化ビニリデン、ポリフッ化ビニリデン−三フッ化塩化エチレン共重合体、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体、ポリエチレンオキシド、ポリプロピレンオキシド、ポリブチレンオキシド、ポリウレタン、ポリアクリロニトリル、ポリアクリレート、ポリメチルメタクリレート、ポリアクリル酸、ポリアクリルアミド、ポリビニルアセテート、ポリビニルピロリドン、ポリテトラエチレングリコールジアクリレート、ポリスルホン、ポリフェニレンオキシド、ポリカーボネート、ポリ塩化ビニリデン、ポリシロキサン、ポリオレフィンアイオノマー及びこれらの共重合体または誘導体からなる群より１種以上選択されるゲル化性高分子を溶媒に溶解してゲル化性高分子溶液を製造する段階;
ｃ）前記ｂ）段階のゲル化性高分子溶液を前記ａ）段階の支持層フィルムの一面または両面に塗布してゲル化性高分子層を形成させて多層フィルムを製造する段階;及び
ｄ）前記ｃ）段階の多層フィルムを延伸して高分子支持層フィルムとゲル化性高分子層に気孔を形成させた後、熱固定する段階
を含む電気化学素子用分離膜の製造方法。a) High density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, highly crystalline polypropylene, polyethylene-propylene copolymer, polyethylene-butylene copolymer, polyethylene-hexene copolymer, polyethylene-octene copolymer , Polystyrene-butylene-styrene copolymer, polystyrene-ethylene-butylene-styrene copolymer, polystyrene, polyphenylene oxide, polysulfone, polycarbonate , polyurethane, polyacrylate, polyvinylidene chloride, polyvinylidene fluoride, polysiloxane, polyolefin ionomer, poly Producing a polymer support layer film selected from the group consisting of methylpentene, hydrogenated oligocyclopentadiene, and copolymers or derivatives thereof. Stage;
b) Polyvinylidene fluoride, polyvinylidene fluoride-trifluoroethylene chloride copolymer, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, polypropylene oxide, polybutylene oxide, polyurethane, polyacrylonitrile, polyacrylate, polymethyl From the group consisting of methacrylate, polyacrylic acid , polyacrylamide, polyvinyl acetate, polyvinyl pyrrolidone, polytetraethylene glycol diacrylate, polysulfone, polyphenylene oxide, polycarbonate , polyvinylidene chloride, polysiloxane, polyolefin ionomer, and copolymers or derivatives thereof. Dissolving one or more selected gelling polymers in a solvent to produce a gelling polymer solution;
c) applying the gelling polymer solution of step b) to one or both sides of the support layer film of step a) to form a gelling polymer layer to produce a multilayer film; and d) A method for producing a separation membrane for an electrochemical element , comprising the step of stretching the multilayer film in step c) to form pores in the polymer support layer film and the gelling polymer layer and then heat-setting. 前記ｃ）段階のゲル化性高分子層の形成は前記ｂ）段階のゲル化性高分子溶液を前記ａ）段階の支持層フィルムの一面または両面に塗布した後、乾燥して実施される、請求項１に記載の電気化学素子用分離膜の製造方法。The formation of the gellable polymer layer in step c) is performed by applying the gellable polymer solution in step b) to one or both sides of the support layer film in step a) and then drying. The manufacturing method of the separation membrane for electrochemical elements of Claim 1. 前記ｃ）段階のゲル化性高分子層の形成は、前記ｂ）段階のゲル化 性高分子溶液を離型フィルム上に塗布して乾燥した後、離型フィルムから剥離して、剥離されたフィルムを前記ａ）段階の支持層フィルムの一面または両面に熱接着して実施される、請求項１に記載の電気化学素子用分離膜の製造方法。In the formation of the gellable polymer layer in the step c), the gellable polymer solution in the step b) was applied on the release film and dried, and then peeled off from the release film. The method for producing a separation membrane for an electrochemical element according to claim 1, which is carried out by thermally bonding the film to one surface or both surfaces of the support layer film in the step a). 前記各々の塗布がディップコーティング、噴射コーティング、スピンコーティング、ダイコーティング、及びロールコーティングからなるコーティング群より選択される方法で実施される、請求項２または３に記載の多電気化学素子用分離膜の製造方法。The separation membrane for a multi- electrochemical device according to claim 2 or 3, wherein each application is performed by a method selected from a coating group consisting of dip coating, spray coating, spin coating, die coating, and roll coating. Production method. 前記各々の乾燥は１乃至１００％の相対湿度、及び窒素、酸素、二酸化炭素、及び空気からなる群より１種以上選択されるガスの雰囲気下で実施される、請求項２または３に記載の電気化学素子用分離膜の製造方法。4. The drying according to claim 2, wherein each drying is performed in an atmosphere of 1 to 100% relative humidity and one or more gases selected from the group consisting of nitrogen, oxygen, carbon dioxide, and air. A method for producing a separation membrane for an electrochemical element . 前記ｄ）段階の延伸は低温延伸した後、高温延伸を実施する、請求項１に記載の多成分系複合フィルムの製造方法。The method for producing a multicomponent composite film according to claim 1, wherein the stretching in the step d) is performed at a low temperature and then at a high temperature. 前記低温延伸はフィルムをロールまたは延伸機で０乃至５０℃の温度条件下で１軸延伸する、請求項６に記載の電気化学素子用分離膜の製造方法。The said low temperature extending | stretching is a manufacturing method of the separation membrane for electrochemical elements of Claim 6 which extends | stretches a film uniaxially on 0-50 degreeC temperature conditions with a roll or a extending machine. 前記高温延伸はフィルムをロールまたは延伸機で５０℃乃至最大に支持層またはゲル化性高分子層の高分子融点の温度下で１軸または２軸延伸する、請求項６に記載の電気化学素子用分離膜の製造方法。The electrochemical device according to claim 6, wherein the high-temperature stretching is performed by uniaxially or biaxially stretching the film at a temperature of a polymer melting point of the support layer or the gelling polymer layer from 50 ° C to a maximum with a roll or a stretching machine. Method for manufacturing a separation membrane . 前記ｄ）段階の熱固定は５０℃乃至最大支持層またはゲル化性高分子層の高分子の融点の温度下でフィルムが張力を受けた状態で１０秒乃至１時間の一定の時間固定して実施される、請求項１に記載の電気化学素子用分離膜の製造方法。The heat setting in the step d) is performed at a fixed time of 10 seconds to 1 hour in a state where the film is under tension at a temperature of 50 ° C. to the maximum melting point of the polymer of the maximum support layer or the gelling polymer layer. The manufacturing method of the separation membrane for electrochemical elements of Claim 1 implemented. 前記高結晶性ポリプロピレンが密度０．９０５ｇ/ｃｃ以上の条件を満足する、請求項１に記載の電気化学素子用分離膜の製造方法。The method for producing a separation membrane for an electrochemical element according to claim 1, wherein the highly crystalline polypropylene satisfies a condition of a density of 0.905 g / cc or more. 前記ａ）段階の支持層フィルムがブレンドフィルムまたは積層フィルムである、請求項１に記載の電気化学素子用分離膜の製造方法。The method for producing a separation membrane for an electrochemical element according to claim 1, wherein the support layer film in the step a) is a blend film or a laminated film. 前記ａ）段階の支持層フィルムが高分子をＴ−ダイまたは円形管ダイが設けられた押出機に投入して押出した後、乾燥オーブンで常温乃至最大支持層の高分子融点の温度下でアニーリングして製造されるフィルムである、請求項１に記載の電気化学素子用分離膜の製造方法。The support layer film in the step a) is extruded at a temperature ranging from room temperature to the polymer melting point of the maximum support layer in a drying oven after the polymer is put into an extruder provided with a T-die or a circular tube die and extruded. The manufacturing method of the separation membrane for electrochemical elements of Claim 1 which is a film manufactured by manufacturing. 前記ａ）段階の支持層フィルムが反応性ガス雰囲気下で支持層フィルムの一面または両面にイオンビームが照射され製造されるフィルムである、請求項１に記載の電気化学素子用分離膜の製造方法。The method for producing a separation membrane for an electrochemical element according to claim 1, wherein the support layer film in step a) is a film produced by irradiating one or both surfaces of the support layer film with an ion beam in a reactive gas atmosphere. . 前記イオンビーム照射が１０−１乃至１０−６ｔｏｒｒの真空度を有する真空槽でヘリウム、水素、酸素、窒素、アンモニア、一酸化炭素、二酸化炭素、クロロフルオロカーボン、メタン、及びＮ２Ｏからなる群より１種以上選択される反応性ガスを０．５乃至２０ml/分の注入量で注入することによって形成される反応性ガス雰囲気下で電子、水素、ヘリウム、酸素、窒素、二酸化炭素、空気、フッ素、ネオン、アルゴン、クリプトン、及びＮ２Ｏからなる群より１種以上選択される粒子を励起して１０−２乃至１０６ｋｅＶのエネルギーを有するものにして生成されたイオンビームを１０５乃至１０２０ｉｏｎｓ/cm2の照射量で照射する、請求項１３に記載の電気化学素子用分離膜の製造方法。A group consisting of helium, hydrogen, oxygen, nitrogen, ammonia, carbon monoxide, carbon dioxide, chlorofluorocarbon, methane, and N 2 O in a vacuum chamber in which the ion beam irradiation has a vacuum degree of 10 −1 to 10 −6 torr. Electron, hydrogen, helium, oxygen, nitrogen, carbon dioxide, air, in a reactive gas atmosphere formed by injecting one or more selected reactive gases at an injection rate of 0.5 to 20 ml / min. An ion beam generated by exciting at least one particle selected from the group consisting of fluorine, neon, argon, krypton, and N 2 O to have an energy of 10 −2 to 10 6 keV is generated from 10 5 to 10 5. The method for producing a separation membrane for an electrochemical element according to claim 13, wherein the irradiation is performed at an irradiation dose of 10 20 ions / cm 2 . 前記ｂ）段階のゲル化性高分子溶液がＬｉＳＣＮ、ＬｉＣｌＯ４、ＬｉＣＦ３ＳＯ３、ＬｉＡｓＦ６、ＬｉＮ（ＣＦ３ＳＯ２）２、及びＬｉＢＦ４からなる群より１種以上選択されるリチウム塩を溶媒にさらに加えて製造される、請求項１に記載の電気化学素子用分離膜の製造方法。In the step b), the gelling polymer solution is a lithium salt selected from the group consisting of LiSCN, LiClO 4 , LiCF 3 SO 3 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , and LiBF 4. The method for producing a separation membrane for an electrochemical element according to claim 1, wherein the separation membrane is produced in addition to a solvent. 前記ｂ）段階のゲル化性高分子溶液がシリカ、酸化チタン、アルミナ、酸化マグネシウム、及び酸化バリウムからなる群より１種以上選択される多孔質無機粒子を溶媒にさらに加えて製造される、請求項１に記載の電気化学素子用分離膜の製造方法。The gelling polymer solution in step b) is produced by further adding porous inorganic particles selected from the group consisting of silica, titanium oxide, alumina, magnesium oxide, and barium oxide to a solvent. Item 2. A method for producing a separation membrane for an electrochemical element according to Item 1. 前記ｂ）段階の溶媒が１−メチル−２−ピロリドン、アセトン、エタノール、ｎ−プロパノール、ｎ−ブタノール、ｎ−ヘキサン、シクロヘキサノール、酢酸、酢酸エチル、ジエチルエーテル、ジメチルホルムアミド、ジメチルアセトアミド、ジオキサン、テトラヒドロフラン、ジメチルスルホキシド、シクロヘキサン、ベンゼン、トルエン、キシレン、水、及びこれらの誘導体からなる群より１種以上選択される、請求項１に記載の電気化学素子用分離膜の製造方法。The solvent in step b) is 1-methyl-2-pyrrolidone, acetone, ethanol, n-propanol, n-butanol, n-hexane, cyclohexanol, acetic acid, ethyl acetate, diethyl ether, dimethylformamide, dimethylacetamide, dioxane, The method for producing a separation membrane for an electrochemical element according to claim 1, wherein at least one selected from the group consisting of tetrahydrofuran, dimethyl sulfoxide, cyclohexane, benzene, toluene, xylene, water, and derivatives thereof. 前記ｂ）段階のゲル化性高分子溶液の濃度が０．０１乃至９０重量％である、請求項１に記載の電気化学素子用分離膜の製造方法。The method for producing a separation membrane for an electrochemical device according to claim 1, wherein the concentration of the gelling polymer solution in step b) is 0.01 to 90% by weight. 前記多成分系複合フィルムは支持層フィルムの気孔の大きさが０．００１乃至１０μｍであり、支持層フィルムの厚さが１乃至５０μｍであり、多孔質ゲル化性高分子層の気孔の大きさが最大１０μｍであり、多孔質ゲル化性高分子層の厚さが０．０１乃至２５μｍである、請求項１に記載の電気化学素子用分離膜の製造方法。The multi-component composite film has a pore size of the support layer film of 0.001 to 10 μm, a thickness of the support layer film of 1 to 50 μm, and a pore size of the porous gelling polymer layer. The method for producing a separation membrane for an electrochemical device according to claim 1, wherein the maximum thickness is 10 µm and the thickness of the porous gelling polymer layer is 0.01 to 25 µm.
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